EP1360223B1 - Certain silicone polyethers, methods for making them and uses - Google Patents

Certain silicone polyethers, methods for making them and uses Download PDF

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Publication number
EP1360223B1
EP1360223B1 EP02701912.4A EP02701912A EP1360223B1 EP 1360223 B1 EP1360223 B1 EP 1360223B1 EP 02701912 A EP02701912 A EP 02701912A EP 1360223 B1 EP1360223 B1 EP 1360223B1
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EP
European Patent Office
Prior art keywords
phenyl
alkyl
substituted
less
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP02701912.4A
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German (de)
English (en)
French (fr)
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EP1360223A2 (en
Inventor
Katherine Clement
Kenneth Lee
Lenin Petroff
Wanda Rauscher
Richard Wehmeyer
Robert Whitmarsh
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Dow Silicones Corp
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Dow Corning Corp
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Publication of EP1360223A2 publication Critical patent/EP1360223A2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

  • This invention relates to certain novel silicone polyethers, and both methods for making and uses for them. More particularly, the invention relates to silicone polyethers based on novel polyethers initiated by certain non-isomerizing alkenyl or alkynyl alcohols, methods for making these silicone polyethers by hydrosilation, and their uses in personal care and other products.
  • Silicone polyethers are used in many applications, notably as surfactants and in the preparation of personal care products, polyurethanes and paint, ink and coating formulations. They may be produced by hydrosilation of a polyether initiated by an aliphatically unsaturated alcohol with a silicone having a SiH functionality.
  • the polyether used may be produced from various initiators and epoxides under the influence of a variety of catalysts. Selection of the exact starting materials and routes utilized is important in determining the properties of the final polymer with even small changes producing very dramatic differences at times. The synthesis chosen for the polyether may be the most critical choice.
  • Alkynyl alcohol initiated polyethers are difficult if not impossible to make using a basic catalyst as there tends to be decomposition of the product, and there is also the issue of migration of the triple bond.
  • Use of Lewis acids solves these problems to some extent, but results in formation of large amounts of difficult to remove byproducts and cyclization of the polyethers.
  • An example in the art showing use of a Lewis acid catalyst in this context is U.S. Patent 3,644,535 to Batty et al. , while U.S. Patent 5,066,756 to Raleigh et al. mentions use of acid and basic catalysts.
  • metal cyanide type catalysts instead of conventional basic or Lewis acid catalysts may improve the situation.
  • Use of cyanide and acid catalysts are described by Burkhart et al. in U.S. Patent No. 5,391,679 for certain specific situations; the silicone was attached to the alcohol first to form the initiator.
  • a similar initiator is described by Watabe et al. in EP 0485637 along with a metal cyanide catalyst, as well as fluorinated polyethers.
  • Jorgenson et al. in U.S Patent Nos. 5,877,268 and 5,856,369 describe use of a metal cyanide catalyst focusing mostly on allyl and methallyl alcohol initiated polyethers; use of metal cyanide catalyst is criticized in some cases there, however.
  • the invention relates to a silicone based polyether comprising a monovalent group, R, with R having an average formula: wherein,
  • the invention relates to a polymer of average formula: wherein
  • the invention relates to a method for making a silicone based polyether, the method comprising:
  • Another object of the present invention is to provide uses for subject silicone based polyethers.
  • the invention further relates to methods for reducing surface tension.
  • the present invention also relates to surfactants and paint, ink and coating formulations, personal care products for treating hair, skin and underarms, as well as polyurethane foams that contain the subject silicone based polyethers.
  • compositions according to the present invention include silicone based polyethers comprising a monovalent group, R, with R having an average formula: wherein,
  • nullity as in "R3 is a nullity” should be taken to mean that group referred to is absent. For example, if R3 is a nullity in-CH2-R3-O-, then this structure is -CH2-O-.
  • halogen should be taken to mean a member of the group consisting of fluorine, chlorine, bromine, iodine and others of this series with chlorine and bromine being preferred.
  • amine group in this same context, should be taken to mean a monovalent group containing nitrogen bonded to at least one organic carbon such as -NHCH3 or -CH2-NH-CH3.
  • Halogen and NO2 containing polymers according to this invention may be desirable for themselves or because they may be converted to NH2 containing polymers by methods such as simple exchange with ammonia or reduction, respectively.
  • These functional groups along with aldehyde, keto and ester functionality can enhance the properties of the simpler polymers of this invention or provide reactive sites for various purposes. Even multifunctional polymers are possible and are often quite desirable in many applications.
  • silicone based polyethers be fully liquid at "room temperature" (25 deg C and 760 mm Hg pressure) as even partial solidification can result in products that are unsightly messes.
  • room temperature 25 deg C and 760 mm Hg pressure
  • lower molecular weight polymers are preferred. In most cases, this translates to an weight average molecular weight for the overall polymer to be less than 10,000 and the equivalent, weight average molecular weight for the polyether/initiator portion to be less than 700.
  • equivalent in this context is meant that this weight is based on the subject polymer side chains (polyether/initiator) as if they were separate molecules.
  • the polydispersity of the overall polymers of the present invention not be very high. Practically speaking, this is usually determined by the polyether/initiator chains. Equivalent polydispersities of the these chains (determined as if these chains were separate molecules) should usually be less 1.6, preferably less than 1.4, more preferably less than 1.25 or less than 1.1 and most preferably less than 1.05 or lower (down to 1.0). These numerical ranges would apply to the polydispersity of the overall silicon based polyether as well.
  • compositions according to the present invention that are of great interest include polymers of average formula: wherein
  • the structural units designated with x' and y' are not necessarily intended as being in blocks as might be implied. That is, these units may be in any order in the chain (except at the ends) as long as there are x' and y' of each, respectively, on average.
  • compositions according to the present invention that are of great interest include polymers of average formula: wherein
  • the methods according to the present invention include those for making silicone based poly ethers, such methods including those comprising: hydrosilating U with a silicone containing an SiH group, where wherein,
  • the hydrosilation reaction is well known in the art. It is usually carried out in the presence of a catalyst such as one based on platinum which are also well known in the art, some examples of which are described below.
  • U be of high purity for hydrosilation.
  • U should be greater than 85 weight percent, preferably U should be greater than 92 weight percent and most preferably U should be greater than 96 weight percent of the material containing U added to the hydrosilation reaction mixture.
  • the initiators for the polyethers used in making the polymers according to the present invention are, at least for the most part, alcohols that contain unsaturated groups that do not (at least usually do not) isomerize. This results in lower odor polymers as it is less likely that smelly products like propionaldehyde will form from them. It is also very efficient to use 1:1 stoichiometric ratios for polyether:silicone in the present hydrosilations in many cases, particularly when using polyethers at lower polydispersities.
  • polyether precursors of the silicone based polyethers of the present invention are believed to be novel and methods for their synthesis (including catalysts used) may be as well. Both are described, at least in part, in co-pending applications assigned or to be assigned to the Dow Chemical Company (and at least in some cases having some common inventors with the present application).
  • Metal cyanide catalysts are suited for making the polyethers used to produce the silicone polyethers of the present invention as has been noted previously. This may be especially true when it is desired to have base sensitive groups in the polyether.
  • DMC catalyst One form of these catalysts (referred to in this specification and the claims that follow as "DMC catalyst") is: M b[ M 1 (CN) r (X) t ] c [M 2 (X) 6 ] d •zL•nM 3 x A y ,
  • DMC catalysts of interest include:
  • catalysts may be insoluble in nonpolar solvents like n-hexane, while the polyethers may be soluble, thus this can be useful in removing the catalyst from the polyether product.
  • Other methods for catalyst removal have been previously described or noted.
  • Another method according to the present invention is a method to reduce the surface tension of a system comprising adding a silicone based polyether of the present invention to the system or a component or components used to produce the system.
  • compositions according to the present invention include those that are also manufactures that contain silicone based polyethers of the present invention.
  • manufactures include surfactants (which could be made solely of a silicone based polyether), personal care products such as treatments for hair, skin or underarms and paint, ink or coating formulations that contain these silicone polyethers, as well as polyurethane foams containing such polyethers as a stabilizer or otherwise.
  • Polydispersity was determined using GPC with a differential refractometer. Samples were prepared by dissolving them in tetrahydrofuran with analysis under the following conditions:
  • a zinc hexacyanocobaltate/t-butanol/450 MW poly(propylene oxide) triol catalyst complex (3.40 g) and 216.40 g of 2-methyl-3-butyn-2-ol are charged to a 2 gallon (7.57 liter) reactor, taking care to transfer all of the catalyst complex into the reactor.
  • the reactor is sealed and degassed/purged several times with nitrogen, with the pressure being maintained above atmospheric pressure at all times to prevent loss of initiator.
  • the mixture is stirred and heated to 90°C.
  • a portion of ethylene oxide (100 g) is added. After one hour, feed of ethylene oxide is started and is fed for 2.5 hours. A total of 845 g ethylene oxide is added.
  • the yield is 1000 g of a light yellow liquid which became opaque (white) upon standing overnight but remained fluid.
  • GPC gel permeation chromatography
  • a polyether may be prepared using the same general procedure as described in Example 1 with 1-chloro-2-methyl-3-butyn-2-ol as the initiator. (Corresponding substituted or functionalized polyethers such as NO2 and NH2 containing or keto functionalized can be made similarly from corresponding initiators and a similar procedure.)
  • the product was devolatilized to a condition of 105 °C at a pressure of 5 mm Hg (667 Pa) to give 74.1 g of copolymer; refractive index was 1.4480.
  • Generation of a Gibb's Plot indicated a CMC (critical micelle concentration) of 4.64E-03 weight percent and a surface tension at CMC of 21.58 dynes/cm (0.0216 N/m).
  • a polysiloxane hydride having the average structure HMe 2 Si(OSiMe 2 ) 13 OSiMe 2 H was combined with 50 g of a polyethyleneoxide having the average structure HC ⁇ CC(Me) 2 (OCH 2 CH 2 ) 6.60 OH (having a polydispersity of about 1.2 as determined by GPC), 0.05 g of sodium acetate and 34 g of isopropyl alcohol. This mixture was heated to 83 °C with enough chloroplatinic acid in isopropyl alcohol to give a level of 12 ppm of platinum metal.
  • the copolymer was devolatilized at 100 °C at a pressure of 5 mm Hg (667 Pa) to give 70.1 g of product; refractive index was 1.4474.
  • Generation of a Gibb's Plot indicated a CMC of 5.08E-03 weight percent and a surface tension at CMC of 21.89 dynes/cm (0.0219 N/m).
  • Example 10 A Silicone Based Polyether With Halogenated Initiator
  • H 2 C CHC(CH 2 Br) 2 (OCH 2 CH 2 ) 9.75 OH as the starting polyether.
  • Corresponding substituted or functionalized silicone based polyethers such as NO2 and NH2 containing or keto functionalized can be made similarly from corresponding polyethers and a similar procedure.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Cosmetics (AREA)
  • Polyethers (AREA)
EP02701912.4A 2001-01-08 2002-01-07 Certain silicone polyethers, methods for making them and uses Expired - Lifetime EP1360223B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/756,440 US20020091219A1 (en) 2001-01-08 2001-01-08 Certain silicone polyethers, methods for making them and uses
US756440 2001-01-08
PCT/US2002/000393 WO2002053625A2 (en) 2001-01-08 2002-01-07 Certain silicone polyethers, methods for making them and uses

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EP1360223A2 EP1360223A2 (en) 2003-11-12
EP1360223B1 true EP1360223B1 (en) 2015-03-04

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EP (1) EP1360223B1 (enrdf_load_stackoverflow)
JP (1) JP2004525205A (enrdf_load_stackoverflow)
CN (1) CN1283696C (enrdf_load_stackoverflow)
AU (1) AU2002235312A1 (enrdf_load_stackoverflow)
WO (1) WO2002053625A2 (enrdf_load_stackoverflow)

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US6987157B2 (en) 2006-01-17
US20020091219A1 (en) 2002-07-11
US20020120087A1 (en) 2002-08-29
AU2002235312A1 (en) 2002-07-16
WO2002053625A3 (en) 2003-02-27
CN1283696C (zh) 2006-11-08
EP1360223A2 (en) 2003-11-12
JP2004525205A (ja) 2004-08-19
CN1582313A (zh) 2005-02-16
WO2002053625A2 (en) 2002-07-11

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